CN1219598C - Catalyst, synthetic method and use thereof - Google Patents
Catalyst, synthetic method and use thereof Download PDFInfo
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- CN1219598C CN1219598C CN 03118779 CN03118779A CN1219598C CN 1219598 C CN1219598 C CN 1219598C CN 03118779 CN03118779 CN 03118779 CN 03118779 A CN03118779 A CN 03118779A CN 1219598 C CN1219598 C CN 1219598C
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Abstract
The present invention discloses a nickel-containing hydrogenation catalyst, a synthetic method thereof and an application thereof. The catalyst is suitable for the catalytic hydrogenation reaction of an aromatic nitro compound and contains the following constituents of the weight percentage: 35 to 60% of nickel measured by nickel oxide, 20 to 45% of aluminium measured by aluminium oxide and 5 to 25% of silicon measured by silicon dioxide, wherein the content sum of the silicon dioxide and the aluminum oxide at least acounts for 30% of the total weight of the catalyst. The preparation method of the catalyst comprises the steps that nickel powder, aluminium powder and a silicon compound are put into a crucible in proportion and are melted to alloy; the alloy is pulverized to less than 200 meshes of particles; the alloy particles are processed by alkaline water solution for 2 to 3 hours and is washed to neutrality by water; then, 15% of sodium bisulfite solution is added and the mixture is stirred for 30 minutes to 1 hour under room temperature; the mixture is stored in 95% of ethanol solution after being washed by water and dried to prepare the catalyst. The present invention overcomes the disadvantages of high cost, high consumption and short service life in the existing nickel-containing hydrogenation catalyst.
Description
Technical field
The present invention relates to a kind of catalyzer, relate in particular to a kind of nickel-containing hydrogenationcatalysts, relate to its synthetic method and application thereof in addition.
Background technology
In the hydrogenation industrial reaction of nickel-containing catalyst through being commonly used in aromatic nitro compound.As document KirKWood.S.et.al; J.Am.Chem.Soc; 69,934, (1947) have been described a kind of method for preparing such nickel-containing catalyst and have been used to prepare the method for aromatic nitro compound hydrogenation with it, and this catalyzer adopts nickel-aluminium alloy to make, and reactive species is handled the back by basic solution and obtained.It is used for, and the aromatic nitro compound hydrogenation is more or less freely to carry out, but required catalytic amount is quite a lot of, and work-ing life is short, and the cost height is difficult to widespread use.
Technical scheme
It is few to the purpose of this invention is to provide a kind of consumption, and long service life (can repeatedly apply mechanically) is applicable to the economically viable novel nickel-containing catalyst of aromatic nitro compound hydrogenation reaction; Another purpose is to provide the synthetic method of this nickel-containing catalyst; Another purpose of the present invention is to provide the application of this nickel-containing catalyst in the aromatic nitro compound catalytic hydrogenation reaction.
This catalyzer contains 35～60% nickel (in nickel oxide), 20～45% aluminium (in aluminum oxide), 5～25% silicon (in silicon-dioxide), its precondition is, the content sum of silicon-dioxide and aluminum oxide should account at least catalyzer gross weight 30%.Optimum ratio is: contain 45～55% nickel (in nickel oxide), and 25～35% aluminium (in aluminium dioxide), 10～25% silicon (in silicon-dioxide), and the content sum of silicon-dioxide and aluminum oxide should account for 30% of total catalyst weight at least.This catalyzer exists with alloy form.
Its synthetic method is as follows: after (1) dropped into crucible in proportion with nickel powder, aluminium powder, silicon compound, the fusion controlled temperature was 1000～1500 ℃ on electric furnace, and 1200～1350 ℃ of preferred temperature are constantly stirred with graphite rod, are incubated 20～30 minutes.(2) pour into then in the large container, slowly cooling has regular crystal structure to guarantee alloy.If cold is too fast, alloy can produce very big stress, makes crystal imperfect.This alloy matter is crisp, be easy to pulverize, so make less than 200 purpose alloy small-particles.(3) handle 2～3 hours after washing to neutral backs of this alloying pellet with alkaline aqueous solution and add 15% sodium sulfite solution, stirred 30 minutes～1 hour under the room temperature, washing is stored in 95% ethanolic soln after straining and doing.Alkaline aqueous solution is generally 25% sodium hydroxide.Generally be used as the starting raw material of preparation catalyzer of the present invention with pure nickel powder, pure aluminium powder, except that water glass, suitable silicon compound is a silicon-dioxide, but water glass is preferred.
Catalyzer of the present invention can be used for the catalytic hydrogenation reaction of organic compound, shortening as nitrile, alkene, aromatic nitro compound, the shortening that is particularly useful for aromatic nitro compound, its aromatic nitro compound is meant nitrobenzene derivative, and nitrobenzene derivative can be that the substituting group on the phenyl ring can have one or more alkyl or hydroxyl or alkoxyl group or amido or halogen except that nitro.With ammonia synthesis gas or hydrogen is sources of hydrogen.
Catalyzer of the present invention has that consumption is few, the characteristics of long service life (can repeatedly apply mechanically), has reduced the production cost of aromatic amine compound preferably; This synthetic method is simple to operate, and is feasible; Prepare in the aromatic nitro compound process at shortening, can use than under the low operating temperature, active suitable, yield is higher.
Embodiment
Embodiment 1 catalyzer of the present invention and preparation thereof
This catalyzer contains following composition: in the nickel of nickel oxide 43%, in the aluminium of aluminum oxide 29%, in the silicon of silicon-dioxide 15%.
In a volume is 500 milliliters asbestos crucible, add 251 gram pure nickel powders, 105 gram aluminium powders and 180 gram water glass, add 164 gram lime carbonate, mixed evenly back heating and melting in SRJX-4 box-shaped resistance furnace, treat that temperature is raised to 1250 ℃, constantly stir, be incubated after 20～30 minutes with graphite rod, pour into then in the large container, slowly cool off to guarantee that alloy has regular crystal structure.Institute's alloyage made slowly to add in the 3000ml 25%NaOH solution behind the small-particle below 200 orders handle this alloying pellet, be washed till neutrality with distilled water after 2～3 hours, add 2000ml 15% sodium sulfite solution then and soak, stirred 1 hour, washing is stored in 95% ethanolic soln after straining and doing.
Embodiment 2 catalyzer of the present invention and preparations thereof
This catalyzer contains following composition: in the nickel of nickel oxide 52%, in the aluminium of aluminum oxide 25%, in the silicon of silicon-dioxide 21%.
In a volume is 500 milliliters asbestos crucible, add 280 gram pure nickel powders, 90 gram aluminium powders and 250 gram water glass, add 80 gram lime carbonate, mixed evenly back heating and melting in SRJX-4 box-shaped resistance furnace, treat that temperature is raised to 1500 ℃, constantly stir, be incubated after 20～30 minutes with graphite rod, pour into then in the large container, slowly cool off to guarantee that alloy has regular crystal structure.Institute's alloyage made slowly to add in the 3000ml 25%NaOH solution behind the small-particle below 200 orders handle this alloying pellet, be washed till neutrality with distilled water after 2～3 hours, add 2000ml 15% sodium sulfite solution then and soak, stirred 30 minutes, washing is stored in 95% ethanolic soln after straining and doing.
Embodiment 3 prepares application in the Ortho Anisidine at the o-Nitrophenyl methyl ether shortening.
It is 1000 milliliters that catalyzer 4 grams that prepare among the embodiment 1 are joined a volume, agitator is installed, well heater, airway, blow-off valve, in the autoclave of pressure and temperature indicating instrument, pack into then 306.3 the gram (2.0 moles) o-Nitrophenyl methyl ethers, reactive system is vacuumized, the inflated with nitrogen displacement, three times so repeatedly, then charge into ammonia synthesis gas, starting agitator reacts down to not obvious absorption hydrogen component (seeing that from tensimeter pointer is motionless) with 5MPa pressure in 140 ℃, stopped reaction, cooling, exhaust, take out reaction mass, the catalyzer of reactor bottom gives over to down to criticize and applies mechanically, and divides oil-yielding stratum in separating funnel, the water layer of draining, underpressure distillation is collected 117～120 ℃/2.67Kpa cut and is got Ortho Anisidine 230 grams, yield 93.8%, and the gas chromatographic analysis product purity is 99.21%.
Embodiment 4 prepares application in the p-phenetidine at the p-Nitrophenetole shortening.
The catalyzer 2 of preparation among the embodiment 1 is restrained in the reaction under high pressure kettle device that joins with embodiment 3, add 167.2 gram (1.0 moles) p-Nitrophenetoles then, select 83.8 gram p-phenetidines to make solvent.With reactive system vacuumize, inflated with nitrogen displacement, three times so repeatedly, then charge into pure hydrogen, start agitator, in 130 ℃, 1.5MPa pressure reaction stopped reaction when no longer absorbing hydrogen down, cooling, exhaust, taking-up reaction mass, the catalyzer of reactor bottom gives over to down to criticize and applies mechanically, in separating funnel, divide oil-yielding stratum, underpressure distillation is collected 130～132 ℃/2.67Kpa fraction and is got p-phenetidine 216.0 grams, deduction feeds intake, and yield is 96.3% after the p-phenetidine that adds, and the gas chromatographic analysis product purity is 99.06%.
Embodiment 5 is catalyzed into application in the hydrogenation reaction at o-Nitraniline
The catalyzer 2 of preparation among the embodiment 2 is restrained in the reaction under high pressure kettle device that joins with embodiment 3, add 138.1 gram (1.0 moles) o-Nitranilines then, 1.2 gram sodium hydroxide, 174 gram water, reactive system is vacuumized, the inflated with nitrogen displacement, three times so repeatedly, then charge into ammonia synthesis gas, begin to stir, in 95 ℃ and 3MPa pressure reaction stopped reaction when no longer absorbing hydrogen down, cooling, exhaust, take out reaction mass, the catalyzer of reactor bottom gives over to down to criticize and applies mechanically, the filtrate air distillation removes and anhydrates, underpressure distillation is collected 115～118 ℃/0.8Kpa fraction and is got O-Phenylene Diamine 100.0 grams then, yield 93.0%, gas chromatographic analysis product purity are 99.33%.
Claims (10)
1, a kind of catalyzer is characterized in that, it contains following composition: in the nickel of nickel oxide 35～60%, in the aluminium of aluminum oxide 20～45%, in the silicon of silicon-dioxide 5～25%, the ratio of each composition all by weight percentage; And the content sum of silicon-dioxide, aluminum oxide should account for 30% of total catalyst weight at least; Catalyzer exists with alloy form.
2, catalyzer as claimed in claim 1 is characterized in that, each composition ratio of this catalyzer is: in the nickel of nickel oxide 45～55%, in the aluminium of aluminum oxide 25～35%, in the silicon of silicon-dioxide 10～25%, the ratio of each composition all by weight percentage.
3, catalyzer as claimed in claim 1 is characterized in that, this alloy is less than 200 purpose particles.
4, the synthetic method of catalyzer as claimed in claim 1, it is characterized in that realize as follows: 1. nickel powder, aluminium powder, silicon compound are put into crucible in proportion, the fusion controlled temperature is 1000～1500 ℃ on electric furnace, hold in both hands constantly stirring with graphite, be incubated 20～30 minutes.2. pour slowly cooling in the container then into, pulverize and make less than 200 purpose small-particle alloys.3. handle this alloy with alkaline aqueous solution and be washed till neutral back adding 15% sodium sulfite solution after 2～3 hours, stirred 30 minutes-1 hour under the room temperature.4. washing is strained driedly, is stored in 95% ethanolic soln.
5, the synthetic method of catalyzer as claimed in claim 4 is characterized in that, the 1. described silicon compound of step is silicon-dioxide or water glass.
6, the synthetic method of catalyzer as claimed in claim 4 is characterized in that, the 1. described fusion controlled temperature of step is 1200～1350 ℃.
7, the synthetic method of catalyzer as claimed in claim 4 is characterized in that, the 3. described alkaline aqueous solution of step is 25% sodium hydroxide.
8, Application of Catalyst as claimed in claim 1 is characterized in that, is being that raw material, ammonia synthesis gas or hydrogen are that sources of hydrogen is made catalyzer in the reaction process of catalytic hydrogenation reaction synthetic aroma amine with the aromatic nitro compound.
9, Application of Catalyst as claimed in claim 8 is characterized in that, described aromatic nitro compound is a nitrobenzene derivative.
10, Application of Catalyst as claimed in claim 9 is characterized in that, nitrobenzene derivative is that the substituting group on the phenyl ring has one or more alkyl or hydroxyl or alkoxyl group or amido or halogen except that nitro.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03118779 CN1219598C (en) | 2003-03-13 | 2003-03-13 | Catalyst, synthetic method and use thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 03118779 CN1219598C (en) | 2003-03-13 | 2003-03-13 | Catalyst, synthetic method and use thereof |
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| CN1530170A CN1530170A (en) | 2004-09-22 |
| CN1219598C true CN1219598C (en) | 2005-09-21 |
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| CN 03118779 Expired - Fee Related CN1219598C (en) | 2003-03-13 | 2003-03-13 | Catalyst, synthetic method and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100441293C (en) * | 2005-09-26 | 2008-12-10 | 天津大学 | Supported nickel catalyst for synthesizing chlora aniline by hydrogenation of chloronitrobenzene and its preparation method thereof |
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